title: Sc3+-triggered oxoiron(IV) formation from O2 and its non-heme iron(II) precursor via a Sc3+-peroxo-Fe3+ intermediate.
abstract: We report that redox-inactive Sc(3+) can trigger O2 activation by the Fe(II)(TMC) center (TMC = tetramethylcyclam) to generate the corresponding oxoiron(IV) complex in the presence of BPh4(-) as an electron donor. To model a possible intermediate in the above reaction, we generated an unprecedented Sc(3+) adduct of [Fe(III)(η(2)-O2)(TMC)](+) by an alternative route, which was found to have an Fe(3+)-(μ-η(2):η(2)-peroxo)-Sc(3+) core and to convert to the oxoiron(IV) complex. These results have important implications for the role a Lewis acid can play in facilitating O-O bond cleavage during the course of O2 activation at non-heme iron centers.
authors.affiliation: Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, Minneapolis, Minnesota 55455, United States.
authors.forename: Feifei
authors.initials: F
authors.lastname: Li
authors.forename: Katherine M
authors.initials: KM
authors.lastname: Van Heuvelen
authors.forename: Katlyn K
authors.initials: KK
authors.lastname: Meier
authors.forename: Eckard
authors.initials: E
authors.lastname: Münck
authors.forename: Lawrence
authors.initials: L
authors.lastname: Que
mesh_terms: D005296:Ferrous Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010100:Oxygen / Q000737:chemistry*; D012538:Scandium / Q000737:chemistry*
chemical_list: D005296:Ferrous Compounds; D009942:Organometallic Compounds; D010100:Oxygen; D012538:Scandium